KR20190129817A - Luminescent Curved Glass and Curved Digital Signage - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides a luminescent curved glass capable of displaying a clear display on the entire surface by irradiating light even though the curvature radius is curved, and providing a curved digital signage using the luminescent curved glass. The purpose. The present invention provides a light-emitting curved glass comprising a laminate of a transparent plate and a light emitting sheet having a radius of curvature of 3000 mm or less, wherein the light emitting sheet includes a thermoplastic resin and a light emitting material that emits visible light having a wavelength of 380 to 750 nm by excitation light. It is luminescent curved glass to contain

Description

Luminescent Curved Glass and Curved Digital Signage

TECHNICAL FIELD The present invention relates to a luminescent curved glass capable of displaying a clear display on the entire surface by irradiating light even though the curvature radius is curved, and a curved digital signage using the luminescent curved glass.

In public facilities such as stations and airports, and commercial facilities such as department stores, digital signage is provided on the display to display various information in moving pictures and still images. In such a digital signage, although a liquid crystal display or a plasma display is generally used (for example, patent document 1, etc.), when a liquid crystal display etc. are used for a large digital signage, it becomes very expensive.

On the other hand, the method of projecting an image from an image projector is employ | adopted using the glass etc. which gave the special process as a screen.

However, in recent years, digital signage of a complicated shape that exhibits higher design is required. Moreover, the installation of the screen of a digital signage is performed using the pillar of a building. When an image is projected on such a complicated screen or a curved screen having a small radius of curvature such as a columnar shape, there is a problem that it is difficult to provide a clear display on the entire surface of the screen.

Japanese Laid-open Patent Publication Hei 4-502525

The present invention has been made in view of the above-described present situation, despite the fact that the radius of curvature is a curved surface with a small radius of curvature, a luminescent curved glass capable of displaying a clear display on the entire surface by irradiating light rays, and a curved digital glass using the luminescent curved glass. It aims to provide signage.

The present invention provides a light-emitting curved glass comprising a laminate of a transparent plate and a light emitting sheet having a radius of curvature of 3000 mm or less, wherein the light emitting sheet includes a thermoplastic resin and a light emitting material that emits visible light having a wavelength of 380 to 750 nm by excitation light. It is a luminescent curved glass to contain.

The present invention is described in detail below.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors irradiate the excitation light to the laminated body which laminated | stacked the light emitting sheet containing the thermoplastic resin and the light emitting material which emits visible light of wavelength 380-750nm by excitation light on the transparent plate. We found out that various images can be displayed. The image is not projected from the image projector but is displayed by the laminate itself emitting light. Therefore, unlike the case of projecting from an image projector, even if the laminate has a curved surface with a small radius of curvature, a clear display can be performed on the entire surface.

The luminescent curved glass of this invention consists of a laminated body of a transparent plate and a light emitting sheet.

The said transparent plate has a role which gives intensity | strength to the luminescent curved glass of this invention, and improves handleability. It is preferable to employ | adopt the structure (plywood glass structure) in which the said light emitting sheet is laminated | stacked among a pair of transparent plates especially as said laminated body.

The transparent plate glass generally used can be used for the said transparent plate. For example, inorganic glass, such as a float plate glass, an abrasive plate glass, a template glass, a reinforcement glass, a standing plate glass, a colored plate glass, a heat ray absorption glass, a heat ray reflection glass, green glass, is mentioned. Moreover, although the ultraviolet shielding glass in which the ultraviolet shielding coat layer was formed in the surface of glass can also be used, it is preferable to use as a glass plate opposite to the side which irradiates the light ray of a specific wavelength. Moreover, organic plastic spans, such as polyethylene terephthalate, polycarbonate, and polyacrylate, can also be used as said transparent plate.

As the transparent plate, two or more kinds of transparent plates may be used. Moreover, you may use the transparent board from which 2 or more types of thickness differ as said transparent board.

The said transparent plate is curvature whose curvature radius is 3000 mm or less. If the radius of curvature is 3000 mm or less, it can be suitably used for digital signage by using a digital signage having a high designability and a pillar of a building. It is preferable that the said transparent board is a curved surface whose curvature radius is 2000 mm or less, and it is more preferable that it is a curved surface whose curvature radius is 1000 mm or less.

Even if the curvature radius of a transparent plate exceeds 3000 mm, the luminous curved glass of this invention can display various images by irradiating an excitation light. However, the present invention has a great advantage in that a clear display can be performed on the entire surface by irradiating light even when the radius of curvature is 3000 mm or less.

Although the thickness of the said transparent plate is not specifically limited, A preferable minimum is 1.5 mm and a preferable upper limit is 15 mm. If the thickness of the said transparent plate is in the said range, sufficient strength and handleability can be compatible. The minimum with more preferable thickness of the said transparent plate is 2.0 mm, and a more preferable upper limit is 12 mm.

The light emitting sheet contains a thermoplastic resin and a light emitting material that emits visible light having a wavelength of 380 to 750 nm by excitation light. By irradiating excitation light to the luminescent curved glass having such a luminescent sheet, the luminescent curved glass itself emits light, and various images can be displayed.

The thermoplastic resin is not particularly limited, and for example, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, polyurethane resin containing elemental sulfur, polyvinyl alcohol resin , Vinyl chloride resin, polyethylene terephthalate resin, and the like. Especially, polyvinyl acetal resin is preferable at the point which can exhibit the outstanding adhesiveness with respect to the said transparent plate by using together with a plasticizer.

The polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by aldehyde acetalization of polyvinyl alcohol, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetals as needed.

The minimum with preferable acetalization degree of the said polyvinyl acetal resin is 40 mol%, a preferable upper limit is 85 mol%, a more preferable minimum is 60 mol%, and a more preferable upper limit is 75 mol%.

The minimum with preferable amount of hydroxyl groups of the said polyvinyl acetal resin is 15 mol%, and a preferable upper limit is 35 mol%. If the amount of hydroxyl groups is 15 mol% or more, the molding of the interlayer film for laminated glass becomes easy. When the amount of hydroxyl groups is 35 mol% or less, handling of the obtained light emitting sheet becomes easy.

In addition, the acetalization degree and the hydroxyl group amount can be measured based on JISK6728 "polyvinyl butyral test method", for example.

The polyvinyl acetal resin can be prepared by aldehyde acetalization of polyvinyl alcohol. The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used.

The minimum with preferable polymerization degree of the said polyvinyl alcohol is 500, and a preferable upper limit is 4000. When the polymerization degree of the said polyvinyl alcohol is 500 or more, the penetration resistance of the laminated glass using the light emitting sheet obtained becomes high. If the polymerization degree of the said polyvinyl alcohol is 4000 or less, shaping | molding of a light emitting sheet will become easy. The minimum with more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.

Although the said aldehyde is not specifically limited, Generally, the C1-C10 aldehyde is used preferably. The aldehyde having 1 to 10 carbon atoms is not particularly limited and includes, for example, n-butylaldehyde, isobutylaldehyde, n-valeraldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, n-octylaldehyde, n- Nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Especially, n-butylaldehyde, n-hexyl aldehyde, n-valeraldehyde is preferable, and n-butylaldehyde is more preferable. These aldehydes may be used independently and may use 2 or more types together.

The light emitting material is a light emitting material that emits visible light having a wavelength of 380 to 750 nm by excitation light. By using such a light emitting material, by emitting excitation light to the luminescent curved glass, the luminescent curved glass itself emits light, and various images can be displayed.

The light emitting material is not particularly limited as long as it emits visible light having a wavelength of 380 to 750 nm by excitation light, and a conventionally known light emitting material can be used. A luminescent material may be used independently and may use 2 or more types together. Among them, a lanthanoid complex having a multidentate ligand containing a halogen atom and a light emitting material having a terephthalic acid ester structure are preferable because it can emit light with high luminance.

Among the lanthanoid complexes, lanthanoid complexes having a multidentate ligand containing a halogen atom emit light with high emission intensity by irradiating light rays. Examples of the lanthanoid complex having a multidentate ligand containing a halogen atom include a lanthanoid complex having a bidentate ligand containing a halogen atom, a lanthanoid complex having a tridentate ligand containing a halogen atom and a 4 containing a halogen atom. The lanthanoid complex which has a left ligand, the lanthanoid complex which has a 5 left ligand containing a halogen atom, the lanthanoid complex which has a 6 left ligand containing a halogen atom, etc. are mentioned.

Especially, the lanthanoid complex which has a bidentate ligand containing a halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom is 580-780 nm by irradiating light of the wavelength of 300-410 nm. The light of wavelength is emitted with very high emission intensity. Since this light emission is very high intensity | strength, the light emitting sheet containing this can fully emit light even in extremely weak excitation light, and can exhibit the very outstanding aesthetic by "shading light emission".

Moreover, the lanthanoid complex which has a bidentate ligand containing the said halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom is also excellent in heat resistance. Therefore, even when the light emitting sheet is used outdoors where the infrared rays of sunlight are irradiated, it can prevent that a light emitting material deteriorates by high temperature.

As used herein, lanthanoid includes lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium. In view of obtaining a higher emission intensity, the lanthanoid is preferably neodymium, europium or terbium, more preferably europium or terbium, still more preferably europium.

The lanthanoid complex having a bidentate ligand containing the above halogen atom is, for example, tris (trifluoroacetylacetone) phenanthroline europium, tris (trifluoroacetylacetone) diphenylphenanthroline europium, tris ( Hexafluoroacetylacetone) diphenylphenanthroline europium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) europium, tris (trifluoroacetylacetone) 2,2'-bipyridine europium, tris (hexa Fluoroacetylacetone) 2,2'-bipyridine europium, etc. are mentioned.

Examples of the lanthanoid complex having a tridentate ligand containing the halogen atom include terpyridine trifluoroacetylacetone europium, terpyridine hexafluoroacetylacetone europium, and the like.

Fluorine atom, chlorine atom, bromine atom, and iodine atom can be used as a halogen atom of the lanthanoid complex which has the said bidentate ligand containing a halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom. Especially, a fluorine atom is preferable at the point which stabilizes the structure of a ligand.

Among the lanthanoid complexes having a bidentate ligand containing a halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom, in particular, the bidentate having a acetylacetone skeleton containing a halogen atom in terms of excellent initial luminescence Preference is given to lanthanoid complexes having ligands.

Lanthanoid complexes having a bidentate ligand having an acetylacetone skeleton containing a halogen atom include, for example, Eu (TFA) ₃ phen, Eu (TFA) ₃ dpphen, Eu (HFA) ₃ phen, [Eu (FOD). ) ₃ ] bpy, [Eu (TFA) ₃ ] tmphen, [Eu (FOD) ₃ ] phen, and the like. The structure of the lanthanoid complex which has a bidentate ligand which has an acetylacetone frame | skeleton containing these halogen atoms is shown.

[Formula 1]

It is preferable that the lanthanoid complex which has a bidentate ligand containing the said halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom is particulate. By being particulate, it is easier to undisperse the lanthanoid complex having a bidentate ligand containing the halogen atom or the lanthanoid complex having a tridentate ligand containing the halogen atom in the light emitting sheet.

When the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is in particulate form, the lower limit of the average particle diameter of the lanthanoid complex is preferably 0.01 µm, and the upper limit is preferably 10. The minimum is more preferable 0.03 micrometer, and a more preferable upper limit is 1 micrometer.

As a light emitting material which has the said terephthalic acid ester structure, the compound which has a structure represented by following General formula (2), and the compound which has a structure represented by following General formula (1) is mentioned, for example.

These may be used independently and may use 2 or more types.

[Formula 2]

In said general formula (1), R <^1> represents an organic group and x is 1, 2, 3, or 4. From the point that transparency of a light emitting sheet becomes further higher, x is 1 or 2, It is more preferable to have a hydroxyl group in 2 or 5 positions of a benzene ring, It has a hydroxyl group in 2 and 5 positions of a benzene ring More preferred.

It is preferable that the organic group of said R <^1> is a hydrocarbon group, It is more preferable that it is a C1-C10 hydrocarbon group, It is more preferable that it is a C1-C5 hydrocarbon group, It is especially preferable that it is a C1-C3 hydrocarbon group. .

When carbon number of the said hydrocarbon group is 10 or less, the light emitting material which has the said terephthalic acid ester structure can be easily disperse | distributed to a light emitting sheet.

It is preferable that the said hydrocarbon group is an alkyl group.

As a compound which has a structure represented by the said General formula (1), diethyl-2, 5- dihydroxy terephthalate, dimethyl-2, 5- dihydroxy terephthalate, etc. are mentioned, for example.

Especially, since the contrast can display a higher image, the compound which has a structure represented by the said General formula (1) is diethyl-2, 5- dihydroxy terephthalate (the Aldrich company "2,5 Diethyl dihydroxy terephthalate ").

In said general formula (2), R <^2> represents an organic group, R <^3> and R <^4> represents a hydrogen atom or an organic group, and y is 1, 2, 3 or 4.

It is preferable that the organic group of said R <^2> is a hydrocarbon group, It is more preferable that it is a C1-C10 hydrocarbon group, It is more preferable that it is a C1-C5 hydrocarbon group, It is especially preferable that it is a C1-C3 hydrocarbon group. .

If carbon number of the said hydrocarbon group is below the said upper limit, the light emitting material which has the said terephthalic acid ester structure can be easily disperse | distributed to a light emitting sheet.

It is preferable that the said hydrocarbon group is an alkyl group.

In said General Formula (2), NR ³ R ⁴ is an amino group.

It is preferable that R <^3> and R <^4> are hydrogen atoms.

Among the hydrogen atoms of the benzene ring of the compound having the structure represented by the general formula (2), one hydrogen atom may be the amino group, two hydrogen atoms may be the amino group, three hydrogen atoms may be the amino group, or four hydrogen atoms. The amino group may be an atom.

As a compound which has a structure represented by the said General formula (2), diethyl-2, 5- diamino terephthalate (made by Aldrich) is preferable at the point which can display an image with a higher contrast.

Although content of the said luminescent material in the said light emitting sheet should just be adjusted suitably according to the kind of luminescent material, the preferable minimum with respect to 100 weight part of said thermoplastic resins is 0.001 weight part, and a preferable upper limit is 10 weight part. When content of the said luminescent material is in this range, it can show the outstanding aesthetic by using together with the said pigment. The minimum with more preferable content of the said luminescent material is 0.01 weight part, a more preferable upper limit is 8 weight part, More preferably, it is 0.1 weight part, and a more preferable upper limit is 5 weight part.

The light emitting sheet may further contain a plasticizer.

The said plasticizer is not specifically limited, For example, organic ester plasticizers, such as monobasic organic acid ester and polybasic organic acid ester, phosphoric acid plasticizers, such as an organic phosphate plasticizer and an organic phosphite plasticizer, etc. are mentioned. It is preferable that the said plasticizer is a liquid plasticizer.

Although the said monobasic organic acid ester is not specifically limited, For example, the glycol ester obtained by reaction of glycol and monobasic organic acid, etc. are mentioned. As said glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, etc. are mentioned, for example. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelagonic acid (n-nonylic acid), and decylic acid. Etc. can be mentioned. Especially, triethylene glycol dicaproic acid ester, triethylene glycol di-2-ethyl butyric acid ester, triethylene glycol di-n-octylic acid ester, triethylene glycol di-2-ethylhexyl acid ester, etc. are preferable.

Although the said polybasic organic acid ester is not specifically limited, For example, the ester compound of polybasic organic acids, such as adipic acid, sebacic acid, azelaic acid, and the alcohol which has a C4-C8 linear or branched structure is mentioned. Can be. Especially, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester, etc. are preferable.

The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, triethylene glycol dicaprylate and triethylene glycol di-n-octanoate , Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adi Pate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyl Rate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene Glycol Dicapriate, Adi Acid dihexyl, dioctyl adipic acid, hexyl cyclohexyl adipic acid, diisononyl adipic acid, heptyl nonyl adipic acid, dibutyl sebaxate, oil-modified sebacic acid alkyd, mixture of phosphate ester and adipic acid ester C6-C8 adipic acid esters, such as a mixed type adipic acid ester produced from a dipic acid ester, a C4-C9 alkyl alcohol, and a C4-C9 cyclic alcohol, hexyl adipic acid, etc. are mentioned.

The said organic phosphate plasticizer is not specifically limited, For example, a tributoxy ethyl phosphate, an isodecyl phenyl phosphate, a triisopropyl phosphate, etc. are mentioned.

Among the above plasticizers, dihexyl adipate (DHA), triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol di-2-ethyl Group consisting of butyrate (3GH), tetraethyleneglycoldi-2-ethylbutylate (4GH), tetraethyleneglycoldi-n-heptanoate (4G7) and triethyleneglycoldi-n-heptanoate (3G7) It is preferable that it is at least 1 sort (s) chosen from.

Moreover, since it is hard to produce hydrolysis as said plasticizer, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH), tetraethylene glycol di-2- It is preferable to contain ethyl hexanoate (4GO) and dihexyl adipate (DHA). It is more preferable to contain tetraethylene glycol di-2-ethylhexanoate (4GO) and triethylene glycol di-2-ethylhexanoate (3GO). It is more preferable to contain triethylene glycol di-2-ethylhexanoate.

Although content of the said plasticizer in the said light emitting sheet is not specifically limited, A preferable minimum with respect to 100 weight part of said thermoplastic resins is 30 weight part, and a preferable upper limit is 100 weight part. If content of the said plasticizer exists in this range, shaping | molding can be made easy without disturbing the aesthetics of a light emitting sheet. The minimum with more preferable content of the said plasticizer is 35 weight part, the more preferable upper limit is 80 weight part, The more preferable minimum is 45 weight part, More preferably, the upper limit is 70 weight part, Especially preferable minimum is 50 weight part, Especially preferable upper limit is 63 Parts by weight.

It is preferable that the said light emitting sheet contains an adhesive force regulator.

As the adhesion force regulator, for example, an alkali metal salt or an alkaline earth metal salt is preferably used. As said adhesive force regulator, salts, such as potassium, sodium, magnesium, are mentioned, for example.

As an acid which comprises the said salt, the organic acid of carboxylic acids, such as octylic acid, hexyl acid, 2-ethylbutyric acid, butyric acid, acetic acid, formic acid, or inorganic acids, such as hydrochloric acid and nitric acid, is mentioned, for example.

In addition, the light emitting sheet may contain potassium, sodium, and magnesium derived from a raw material such as a neutralizer used in manufacturing a thermoplastic resin, in addition to the adhesive force adjusting agent. When there is much content of these metals, the light emission property of a light emitting material may fall. This deterioration in luminescence is particularly remarkable when the luminescent material is a lanthanoid complex having a bidentate ligand containing the halogen atom or a lanthanoid complex having a tridentate ligand containing the halogen atom.

Therefore, it is preferable that content of the sum total of potassium, sodium, and magnesium contained in a light emitting sheet is 50 ppm or less. By making content of the sum total of potassium, sodium, and magnesium into 50 ppm or less, it can prevent that the luminescence of a light emitting material falls.

It is preferable that the said light emitting sheet contains a dispersing agent further. By containing a dispersing agent, aggregation of the said luminescent material can be suppressed.

The said dispersing agent is ester, such as a compound which has sulfonic acid structures, such as a linear alkylbenzene sulfonate, a diester compound, a ricinolic acid alkyl ester, a phthalic ester, adipic acid ester, a sebacic acid ester, and a phosphate ester, for example. A compound having a structure, a compound having an ether structure such as polyoxyethylene glycol, polyoxypropylene glycol, alkylphenyl-polyoxyethylene-ether, a compound having a carboxylic acid structure such as polycarboxylic acid, or lauryl Compounds having an amine structure such as amine, dimethyl laurylamine, oleylpropylenediamine, secondary amine of polyoxyethylene, tertiary amine of polyoxyethylene, diamine of polyoxyethylene, polyalkylene polyamine alkylene oxide and the like. Amide structures such as a compound having a polyamine structure and an oleic acid diethanolamide, an alkanol fatty acid amide And dispersing agents such as compounds having a high molecular weight amide structure such as polyvinylpyrrolidone and polyester acid amide amine salt. Moreover, you may use high molecular weight dispersing agents, such as polyoxyethylene alkyl ether phosphoric acid (salt), high molecular polycarboxylic acid, and condensation ricinolic acid ester. In addition, a high molecular weight dispersant is defined as the dispersing agent whose molecular weight is 10,000 or more.

The dispersant with respect to 100 parts by weight of the luminescent material in the luminescent sheet when the luminescent material is a lanthanoid complex having a bidentate ligand containing the halogen atom or a lanthanoid complex having a tridentate ligand containing the halogen atom The minimum with preferable content of is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said dispersing agent is in this range, the lanthanoid complex which has a bidentate ligand containing the said halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom can be disperse | distributed uniformly in a light emitting sheet. The minimum with more preferable content of the said dispersing agent is 3 weight part, a more preferable upper limit is 30 weight part, More preferably, a minimum is 5 weight part, and a more preferable upper limit is 25 weight part.

The said light emitting sheet may contain additives, such as a ultraviolet absorber, antioxidant, a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye, as needed.

The luminescent curved glass of the present invention can give a clear display on the entire surface by being irradiated with excitation light of the luminescent material, even though the curvature radius is curved. Therefore, it can be used suitably for digital signage using the digital signage of the complex shape with high designability, and the pillar of a building.

The light source and the curved digital signage which consists of the luminescent curved glass of this invention are also one of this invention.

According to the present invention, despite the curved surface having a small radius of curvature, it is possible to provide a luminescent curved glass capable of displaying a clear display on the entire surface by irradiating light rays, and a curved digital signage using the luminescent curved glass. Can be.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the method which displays character information in evaluation of an Example and a comparative example.

Although an Example is given to the following and the aspect of this invention is demonstrated in more detail, this invention is not limited only to these Examples.

(Example 1)

(1) Preparation of Eu (TFA) ₃ phen

12.5 mmol of europium acetate (Eu (CH ₃ COO) ₃ ) is dissolved in 50 ml of distilled water, 33.6 mmol of trifluoroacetylacetone (TFA, CH ₃ COCH ₂ COCF ₃ ) is added, and stirred at room temperature for 3 hours. It was. The precipitated solid was filtered, washed with water, and then recrystallized with methanol and distilled water to obtain Eu (TFA) ₃ (H ₂ O) ₂ . 5.77 g of the obtained complex Eu (TFA) ₃ (H ₂ O) ₂ and 2.5 g of 1,10-phenanthroline (phen) were dissolved in 100 mL of methanol, and heated to reflux for 12 hours. After 12 hours, methanol was removed by distillation under reduced pressure to obtain a white product. After washing this powder with toluene and removing the unreacted raw material by suction filtration, toluene was distilled off under reduced pressure and the powder body was obtained. Eu (TFA) ₃ phen was obtained by recrystallization with a mixed solvent of toluene and hexane.

(2) Preparation of light emitting sheet

To 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, 0.2 parts by weight of Eu (TFA) ₃ phen as a light emitting material and acetylacetone magnesium were added so that the final concentration was 0.036 phr as the adhesion regulator. In addition, the luminescent plasticizer solution was prepared. The total amount of the obtained plasticizer solution and 100 parts by weight of polyvinyl butyral (PVB, polymerization degree 1700) were sufficiently kneaded with a mixing roll to prepare a resin composition.

The obtained resin composition was extruded using the extruder and the light emitting sheet of 760 micrometers in thickness was obtained.

(3) Preparation of Luminescent Curved Glass

The obtained light emitting sheet was laminated | stacked between a pair of clear glass (thickness 2.5mm and curvature radius 3000mm) of a pair of 30 cm x 30 cm width, and the laminated body was obtained. The obtained laminated body was vacuum-pressed and crimped | bonded, holding | maintaining at 90 degreeC for 30 minutes with a vacuum laminator. After crimping | bonding was crimped | bonded for 20 minutes using the autoclave on 140 degreeC and 14 Mpa conditions, the luminescent curved glass of the laminated glass structure was obtained.

(Example 2)

A light emitting sheet and a luminescent curved glass were produced in the same manner as in Example 1 except that a pair of clear glass having a thickness of 2.5 mm and a curvature radius of 2000 mm was used.

(Example 3)

A light emitting sheet and a luminescent curved glass were produced in the same manner as in Example 1 except that a pair of clear glass having a thickness of 2.5 mm and a curvature radius of 1000 mm was used.

(Example 4)

12.5 mmol of terbium acetate (Tb (CH ₃ COO) ₃ ) was dissolved in 50 mL of distilled water, and 33.6 mmol of trifluoroacetylacetone (TFA, CH ₃ COCH ₂ COCF ₃ ) was added thereto, followed by stirring at room temperature for 3 hours. It was. The precipitated solid was filtered, washed with water, and then recrystallized with methanol and distilled water to obtain Tb (TFA) ₃ (H ₂ O) ₂ . 5.77 g of the obtained complex Tb (TFA) ₃ (H ₂ O) ₂ and 2.5 g of 1,10-phenanthroline (phen) were dissolved in 100 ml of methanol, and heated to reflux for 12 hours. After 12 hours, methanol was removed by distillation under reduced pressure to obtain a white product. After wash | cleaning this powder with toluene and removing the unreacted raw material by suction filtration, toluene was distilled off under reduced pressure and powder was obtained. Tb (TFA) ₃ phen was obtained by recrystallization with a mixed solvent of toluene and hexane.

A light emitting sheet and a luminescent curved glass were prepared in the same manner as in Example 1 except that Tb (TFA) ₃ phen was used instead of Eu (TFA) ₃ phen.

(Example 5)

Light emission was carried out in the same manner as in Example 1, except that diethyl-2,5-dihydroxyterephthalate ("2,5-dihydroxyterephthalate diethyl" manufactured by Aldrich) was used instead of Eu (TFA) ₃ phen. A sheet, a luminescent curved glass, was prepared.

(Comparative Example 1)

A resin sheet and curved glass were produced in the same manner as in Example 1 except that no light emitting material was used.

(evaluation)

About the luminescent curved glass obtained by the Example and the comparative example, it evaluated by the following method.

The results are shown in Table 1.

As shown in FIG. 1, the light of wavelength 405nm and the output of 1 Hz is irradiated from the center point side of the curved surface of the luminescent curved glass obtained by the Example using an image projector (made by OPUS, ePro-2000) as an excitation light source, By emitting the light emitting material, "A" was displayed at nine points as character information.

On the other hand, green light with a wavelength of 515 nm was irradiated from the center point of the curved surface of the curved glass obtained in Comparative Example 1 using an image projector (ePro-2000, manufactured by OPUS), and "A" was displayed at nine points as character information. I was.

Each "A" was visually observed and the case where "A" in which deformation was confirmed was less than five, and the case where "A" in which deformation was confirmed was five or more was evaluated as "x".

Industrial availability

According to the present invention, despite the curved surface having a small radius of curvature, it is possible to provide a luminescent curved glass capable of displaying a clear display on the entire surface by irradiating light rays, and a curved digital signage using the luminescent curved glass. Can be.

Claims (5)

A luminescent curved glass comprising a laminate of a transparent plate and a light emitting sheet having a radius of curvature of 3000 mm or less,
The said light emitting sheet contains a thermoplastic resin and the light emitting material which emits visible light of wavelength 380-750 nm by excitation light, The luminescent curved glass characterized by the above-mentioned. The method of claim 1,
The curvature radius of a transparent plate is 2000 mm or less, The luminous curved glass characterized by the above-mentioned. The method of claim 1,
The curvature radius of a transparent plate is 1000 mm or less, The luminous curved glass characterized by the above-mentioned. The method according to claim 1, 2 or 3,
A luminescent curved glass comprising a laminate in which a light emitting sheet is laminated between a pair of transparent plates. The curved digital signage which consists of a light source and the luminescent curved glass of Claim 1, 2, 3, or 4.

Images